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1 Electronic supporting informtion Post-polymeriztion functionliztion of liner polyglycidol with diethyl vinylphosphonte Jens Köhler, Helmut Keul* nd Mrtin Möller* Institute of Technicl nd Mcromoleculr Chemistry, RWTH Achen University nd DWI n der RWTH Achen e.v., Puwelsstrsse 8, 5056 Achen, Germny. * Correspondence to: H. Keul, Emil: keul@dwi.rwth-chen.de M. Möller, Emil: moeller@dwi.rwth-chen.de S

2 Experimentl Mterils Bromotrimethylsilne (98 %, ABCR), potssium tert-utoxide ( M solution in THF, Aldrich), N,N-Dimethylformmid s., over moleculr sieves (Aldrich), chloroform p.. (VWR) nd methnol p.. (VWR) were used s received. Diethyl vinylphosphonte (95 + %, Aldrich) ws stirred with clcium hydride for 4 h, distilled under reduced pressure nd stored under nitrogen in Schlenk flsk. 3-Phenyl--propnol (3-PP) ( 98%, Fluk) ws rected with smll mounts of sodium nd distilled. Diglyme ws distilled over sodium efore use. Ethoxy ethyl glycidyl ether (EEGE) ws synthesized from,3-epoxypropn--ol (glycidol) nd ethyl vinyl ether ccording to Fitton et l., purified y distilltion nd stored under nitrogen tmosphere over moleculr sieves (4 Å). The syntheses of Poly(ethoxy ethyl glycidyl ether) (P(EEGE)) ()nd polyglycidol (PG) () were perfomed ccording to Hns et l. All rections were crried out in nitrogen tmosphere unless otherwise noted. Nitrogen (Linde 5.0) ws pssed over moleculr sieves (4 Å) nd finely distriuted potssium on luminium oxide. The results of the chemicl nlysis for P(EEGE)() nd PG ()re summrized in Tle S. Tle S. Rtio of monomer to inititor djusted in the feed, degree of polymeriztion (P n ) nd moleculr weight (M n ) determined y end group nlysis ( H NMR) nd SEC dt of liner P(EEGE)()nd PG (). polymer [EEGE]/[3-PP] P n M n M n M w /M n yield / (g/mol) (g/mol) % P(EEGE) () PG () Degree of polymeriztion (P n) nd moleculr weight (M n) clculted from H NMR. Moleculr weight nd moleculr weight distriution determined y size exclusion chromtogrphy (SEC) in THF s eluent for P(EEGE) nd DMF s eluent for PG. Nrrow distriuted poly(methyl methcrylte) stndrds nd were used for clirtion. S

3 Mesurements H NMR, 3 C NMR nd proton decoupled 3 P NMR spectr ( 3 P{ H}) were recorded on Bruker DPX-400 FT-NMR spectrometer t 400 MHz nd 0 MHz nd 6 MHz, respectively. Deuterted chloroform (CDCl 3 ) or dimethyl sulfoxide (DMS-d 6 ) were used s solvents. TMS served s internl reference for CDCl 3.Spectr recorded in DMS-d 6 were referenced ginst the solvent signl (DMS-d 6 : (ppm) =.50). 3 P{ H} NMR spectr were referenced ginst 85 % H 3 P 4 s externl reference. The coupling constnts J xy re given in Hz. Moleculr weights (M n nd M w ) were determined y size exclusion chromtogrphy (SEC). SEC nlyses were crried out with THF, DMF or wter s eluent. For THF SEC high pressure liquid chromtogrphy pump (ERC 640) with RI detector (WGE Dr. Bures ETA 00) t 30 C ws used. The eluent ws THF HPLC grde nd flow rte of.0 ml/min ws used. Four columns with MZ SDplus gel were pplied. Length of ech column ws 300 mm, dimeter 8 mm nd nominl pore widths were 50, 00, 000, 0000 Å. The clirtion ws chieved with commercil poly(methyl methcrylte) stndrds. For DMF SEC high pressure liquid chromtogrphy pump (Bischoff HPLC Compct Pump) with RI detector (Jsco RI-03plus) t 30 C ws used. The eluent ws DMF optigrde with mg/ml LiBr nd flow rte of.0 ml/min ws used. Three columns with PSS GRAM gel were pplied. Length of ech column ws 300 mm, dimeter 8 mm nd nominl pore widths were 00, 000, 3000 Å. Nrrow distriuted poly(methyl methcrylte) stndrds were used for clirtion. Wter SEC is using high pressure liquid chromtogrphy pump (Agilent Series 00) with RI detector (ptil DSP) t 30 C. The eluent ws H HPLC grde nd flow rte of.0 ml/min ws used. Three columns with PSS SUPREMA gel were pplied. Length of ech column ws 300 mm, dimeter 8 mm nd nominl pore widths were 30, 000, 3000 Å. The clirtion ws chieved with commercil poly(ethylene glycol) stndrds. Results were evluted using the PSS WinGPC Unity softwre. S3

4 Syntheses Synthesis of liner poly[(glycidol-diethylphosphontoethyl)-co-glycidol] P[(G DEPE )-co-g] (3d) H H x+y P Polyglycidol () (0.579 g, mmol) ws dissolved in DMF ( ml) nd potssium tertutoxide (0.35 ml of M solution in THF, 0.35 mmol) ws dded over h using syringe pump. Upon ddition of the lkoxide, smll mount of insolule cogulte ws formed, which ws identified s potssium slt of polyglycidol. The solution ws stirred for 30 minutes t room temperture. The tert-utnol formed ws removed y distilltion. Diethyl vinylphosphonte (0.874 g, 5.38 mmol) ws dded nd the mixture ws stirred for 44 h t room temperture. The cogulte ws removed y filtrtion nd the product ws dried in vcuum. The residue ws redissolved in chloroform nd precipitted in cold pentne. A rownish viscous liquid ws otined. (3d)Yield:.06 g (70 %). H NMR (DMS-d 6 ):.3 (tr, 6H, 3 J HH = 7.0 Hz, PCH CH 3 ),.78 (quin, H, 3 J HH = 7.00 Hz, ArCH CH ),.05 (dtr, H, 3 J HH = 7.7 Hz, J HP = 8.3 Hz, CH CH CH P),.6 (tr, H, 3 J HH = 7.66 Hz, ArCH ), (m, 4H, ArCH CH CH, CH CH(CH H), CH CH(CH CH CH P)), (m, 4H, PCH CH 3 ), 4.57 (r s, CH CH(CH H)), (m, 3H, Ar), (m, H, Ar). 3 C NMR (DMS-d 6 ): 6. (d, 3 J CP = 5.8 Hz, PCH CH 3 ), 6.0 (d, J CP = 37 Hz, CH CH CH P), 3.0 (ArCH CH ), 3.6 (ArCH ), 6.0, (PCH CH 3, CH CH(CH H)), 64.8 (CH(CH CH CH P)), (ArCH CH CH, CH CH(CH CH CH P), CH CH(CH H)), 78., 78. (CH CH(CH CH CH P)), 80., 80. (CH CH(CH H)), 5.7 (Ar), 8.3 (Ar), 4. (Ar). 3 P NMR (DMS-d 6 ): 8.5. The synthesis of P[(G DEPE )-co-g] (3,,c) ws performed in nlogy to 3d. Regent rtios, rection conditions nd yields otined fter purifiction re listed in Tle S. For nlyticl S4

5 dt of the product see Tle S3. The conversion of hydroxy groups vs. rection time is shown in Figure S4. Tle S. Synthesis of liner P[(G DEPE )-co-g](3-d): Regent rtios, rection conditions nd yields otined fter purifiction. PG / K t Bu / DEVP / t / yield / Polymer g, (mmol) ml, (mmol) g, (mmol) h % , (0.4) 0.08, (0.08) 0.93,(.8) , (0.3) 0.6, (0.6) 0.4, (.50) c 0.477, (0.9) 0.9, (0.9) 0.480,(.9) d 0.579, (0.36) 0.35, (0.35) 0.874,(5.33) M solution in THF. 6.5 Mol.-% reltive to the mount of DEVP. precipittion in cold pentne. Yield fter purifiction y Tle S3. Rtios of DEVP to hydroxy groups in the feed, degree of functionliztion F (percentge of phosphonoethyltion), numer verge moleculr weights determined y H NMR nd SEC nd moleculr weight distriution of P[(G DEPE )-co-g] (3-d). polymer rtio F NMR M n, NMR M n, SEC M w /M n, SEC [DEVP]/[H] (%) (g/mol) (g/mol) c d According to H NMR nlysis. Devition from the djusted rtio due to integrtion error. Moleculr weight nd moleculr weight distriution determined y size exclusion chromtogrphy (SEC) using nrrow distriuted poly(methyl methcrylte) stndrds nd DMF s eluent. Formul used for the clcultion of the degree of functionliztion F y H NMR nlysis: S5

6 7 H H 0 x+y= 4 3 P F(%) 5 I() 00 I (,,3) x y I (): Intensity of the signl. Assignment sed on the structure shown ove. x+y: Totl numer of repeting units In Figure S the conversion of hydroxy groups within polyglycidol is plotted ginst the rection time. Figure S. Phosphonoethyltion of polyglycidol with DEVP: Conversion of hydroxy groups( in %) s function of time for different regent rtios (see Tle S3). Identifiction of diethyl--ethoxyethyl phosphonte s side-product fter vrition of the rection conditions: S6

7 The P[(G DEPE )-co-g]s (3-d) were purified y precipittion in cold pentne. In Figure Sthe H nd 3 P NMR spectr of the mother liquor re shown for the ddition of PG to DEVP in DMF s solvent ctlyzed y 3 mole-% K t Bu t 70 C(These rection conditions led to incresed cogultion nd rodening of the moleculr weight distriution).diethyl-- ethoxyethyl phosphonte ws found s side-product under this rection condition. 3 4 P Figure S. H (top) nd 3 P NMR spectrum (ottom) recorded in CDCl 3 of the pentne phse of rection performed t 70 C with 3 Mole-% of the lkline ctlyst (rection is not included in this communiction). H NMR (CDCl 3 ):.3 (tr, 3H, 3 J HH = 7.0 Hz, CH 3 CH CH ),.6 (tr, 6H, 3 J HH = 7.07 Hz, PCH CH 3 ),.04 (dtr, H, 3 J HH = 7.5 Hz, J HP = 8.7 Hz, CH CH CH P), 3.43 (q, H,, 3 J HH = 7.0 Hz CH 3 CH CH ), 3.6 (dtr, H, 3 J HH = 5.80 Hz, J HP =.6 Hz, CH CH CH P), (m, 4H, PCH CH 3 ). ). 3 C NMR (DMS-d 6 ): 5. (CH 3 CH CH ), 6.4 (d, 3 J CP = 6. Hz, PCH CH 3 ), 7. (d, J CP = 39 Hz, CH CH CH P), 6.6 (d, J CP = 6. Hz, PCH CH 3 ), 64.4 (CH 3 CH CH ), 66.3 (CH 3 CH CH ). 3 P NMR (DMS-d 6 ): 8.8. S7

8 Synthesis of liner poly[(glycidol-phosphontoethyl)-co-glycidol]; P[(G PE )-co-g] (4d) H P H H H x+y P[(G DEPE )-co-g] (3d) (0.495 g,.773 mmol,.774 mmolof phosphonte) ws dissolved in chloroform nd cooled to 0 C. Four equivlents of romotrimethylsilne (0.9 ml, mmol) were dded dropwise to the solution. After complete ddition of the silylting gent, the ice th ws removed nd the mixture ws stirred for 7 h t room temperture. The solvent nd other voltile yproducts were removed in vcuum. The residue otined ws dissolved in methnol (0 ml) nd stirred for 4 h t room temperture. The solvent ws removed y distilltion nd the product ws tken up in wter nd purified y centrifugtion. (4d)Yield: g, (90 %). H NMR (DMS-d 6 ):.77 (quin, H, 3 J HH = 6.9 Hz, ArCH CH ),.90 (r s, H, CH CH CH P),.60 (tr, H, 3 J HH = 7.65 Hz, ArCH ), (m, 4H, ArCH CH CH, CH CH(CH H), CH CH(CH CH CH P)), 5.6 (r s, 3H, CH(CH H), PH), (m, 3H, Ar). 3 C NMR (DMS-d 6 ): 8.6 (d, J CP = 34 Hz, CH CH CH P), 3.6 (ArCH ), 60.8, 60.9 (CH CH(CH H)), 65.4 (CH(CH CH CH P)), (ArCH CH CH, CH CH(CH CH CH P), CH CH(CH H)), 78.0, 78. (CH CH(CH CH CH P)), 80., 80. (CH CH(CH H)), 5.7 (Ar), 8.3, 8.4 (Ar). The signl for the quternry cron of the phenyl ring nd the signl for CH CH CH could not e distinguished from the noise of the seline. 3 P NMR (DMS-d 6 ): 3.9. The synthesis of P[(G PE )-co-g] (4,,c) ws performed in nlogy to 4d. Regent rtios, rection conditions nd yields otined fter purifiction re listed in. For nlyticl dt see. S8

9 Tle S4. Synthesis of liner P[(G PE )-co-g](4-d): Regents, rection times nd yields. Polymer P(G DEPE -co-g)/ TMS-Br / time / yield / g, (mmol, mmol phosphonte) ml, (mmol) h % , (.80, 0.764) 0.40, (3.057) , (3.080, 0.980) 0.5, (3.90) c 0.534, (3.40,.70) 0.56,(4.75) d 0.495, (.773,.774) 0.9, (7.056) 7 90 Tle S5.Synthesis of P[(G PE )-co-g] (4-d): Degree of functionliztion nd moleculr weights determined from H NMR nd moleculr weights nd moleculr weight distriution determined y SEC nlysis. polymer F NMR M n, NMR M n, SEC M w /M n, SEC (%) (g/mol) (g/mol) c d According to H NMR nlysis. Moleculr weight nd moleculr weight distriution determined y SEC using nrrow distriuted poly(ethylene glycol) stndrds nd wter s eluent. S9

10 Figure S3shows the comprison of 3 P NMR spectr of P[(G DEPE -co-g)] (3d)nd P[(G PE -co- G)](4d). P[(G DEPE )-co-g] P[(G PE )-co-g] Figure S3. Comprison of 3 P NMR spectr of P[(G DEPE -co-g)] nd P[(G PE -co-g)] recorded in DMSd 6. A comprison of the 3 C NMR spectr of PG, P[(G DEPE -co-g)] (3d)nd P[(G PE -co-g)] (4d)is shown in Figure S H 0 H, ,3,3 7 H H 3, ,8 3 P 6 9 0, H H ,8 H 9 0,5 7 5 P 6 H Figure S4. Comprison of 3 C NMR spectr of PG (top), P[(G DEPE -co-g)] (middle) nd P[(G PE -co-g)] (ottom) recorded in DMS-d 6. References A.. Fitton, J. Hill, D. E. Jne, R. Millr, Synthesis-Stuttgrt, 987,, 40. S0

11 M. Hns, P. Gsteier, H. Keul, M. Moeller, Mcromolecules, 006, 39, 384. S